CN1049529C - Cathode material for lithium secondary battery and method of manufacturing the same - Google Patents
Cathode material for lithium secondary battery and method of manufacturing the same Download PDFInfo
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- CN1049529C CN1049529C CN94117559A CN94117559A CN1049529C CN 1049529 C CN1049529 C CN 1049529C CN 94117559 A CN94117559 A CN 94117559A CN 94117559 A CN94117559 A CN 94117559A CN 1049529 C CN1049529 C CN 1049529C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The present invention relates to a cathode material for a lithium secondary battery and a method of manufacturing the same. The lithium manganese composite oxide is XLiMn 2 O 4 MnO of Y gamma and/or beta 2 X is more than or equal to 0.5Y, X is more than or equal to 1 and less than or equal to 4, and the LiMn is spinel-type LiMn 2 O 4 With gamma and/or beta MnO 2 Composite oxide of (2)I/I of peaks at 21 DEG and 19 DEG in X-ray diffraction spectrum o The ratio of (A) to (B) is 1: 1-1.7, and the relative intensity of the peak at 57 DEG is 30 & lt I/I o Is < 70. The preparation method is to add MnO 2 And lithium compound in Li to Mn ratio =1 to 2.2-4.0, and maintaining at 200-400 deg.c in flowing air for 10-40 hr. The product has high specific capacity and excellent cycle performance. The preparation method has simple process.
Description
The present invention relates to an electrode material and a method for preparing the same, and more particularly, to a cathode material for a lithium secondary battery and a method for preparing the same.
Manganese dioxide is an inexpensive material that is widely used in zinc manganese batteries, lithium manganese batteries, and alkaline manganese batteries as an active cathode material for the batteries. However, the single manganese dioxide has no reversibility of charge and discharge in the above batteries, and in order to solve the reversibility of manganese dioxide, rechargeable lithium batteries have been developed, and manganese dioxide is generally modified with a lithium-containing compound, and examples of manganese dioxide used for modification include Electrolytic Manganese Dioxide (EMD) and Chemical Manganese Dioxide (CMD). Among these two manganese dioxide, electrolytic Manganese Dioxide (EMD) has low price, large specific gravity and high activity, and is advantageous for reaction with lithium salt.
Japanese patent laid-open No. 5-174822 discloses that lithium hydroxide and manganese dioxide are mixed and heated at 250-400 deg.C to synthesize lithium manganese composite oxide, the molar ratio of Li to Mn is 1: 2.4-3.3, the X-ray peak value 2 theta angle is 19 deg., 21 deg., 33 deg., 37 deg., 42 deg., 53 deg., 66 deg., and the peak intensity ratio of 21 deg. and 19 deg. is I/I o (21°)∶I/I o (19 °) = 1: 0.7-1: 1.2. The material is synthesized by adopting lithium hydroxide aqueous solution and Electrolytic Manganese Dioxide (EMD), or lithium hydroxide obtained by neutralizing lithium salt by adopting ammonium hydroxide and EMD, and the specific surface area of EMD is 30-100 m 2 (iv) g. The obtained lithium-manganese composite oxide is used for button lithium secondary batteries, (phi 16mm multiplied by 0.4 mm), the cathode components are LixMnOy100%, and graphite Wt.5%. Adhesive: 60% concentration of polytetrafluoroethylene Wt.2%, anode of 40% (atomic percent) lithium-aluminum alloy, and electrolyte of 1MLiClO 4 In thatPC (propylene carbonate) and DME (ethylene glycol dimethyl ether). The charge-discharge range is 3.25V-2.0V.
Nohma et al (J.PowerSources 26, 389.1989) have used EMD and LiOH to thermally synthesize lithium manganese complex oxide, the product of which is Li 2 MnO 3 And gamma/beta MnO 2 The capacity of the composite oxide is low, and is only 120-140mAh/g, wherein the composite oxide is Li 2 MnO 3 Is not reversible.
The invention aims to develop a novel high-capacity lithium-manganese composite oxide, which has large specific capacity, high discharge capacity and greatly increased 50% deep cycle times and is used as a cathode material of a lithium secondary battery.
Another object of the present invention is to develop a process for preparing the above-mentioned lithium manganese composite oxide for a cathode material of a lithium secondary battery, which has excellent properties such as high specific capacity.
A lithium manganese composite oxide for a cathode active material of a lithium secondary battery of the present invention, the compositeThe mixed oxide is XLIMn 2 O 4 Y γ and/or β MnO2, X is not less than 0.5Y, X is not less than 1 and not more than 4, and the structure is spinel-type LiMn 2 O 4 With gamma and/or beta MnO 2 The X-ray diffraction structural analysis of CuK α incidence shows that 2 θ:19 °,21 °, 29 °, 37 °, 57 °; relative intensity of peaks 21 DEG and 19 DEG (I/I) o ) The ratio of (1: 1) - (1.7), the relative intensity of the peak at 2 theta =57 DEG is 30 < I/I o ＜70。
The lithium manganese compound with high capacity is spinel LiMn 2 O 4 With gamma and/or beta MnO 2 A composite oxide of, r-MnO 2 Is stabilized by Li, not only has higher capacity, but also has better reversibility of lithium ion insertion and extraction.
For lithium secondary batteryThe preparation method of cathode active material lithium manganese composite oxide is characterized by that it uses one of lithium compound of lithium hydroxide, lithium nitrate and lithium oxalate and manganese dioxide, and fully mixes them according to the atomic ratio of Li to Mn = 1: 2.2-4.0, then the mixture is heat-insulated in flowing air at 200-400 deg.C for 10-40 hr, and synthesized to form product XLIMn 2 O 4 Y gamma and/or beta MnO2, X is more than or equal to 0.5Y, X is more than or equal to 1 and less than or equal to 4.
In order to sufficiently and uniformly mix the manganese dioxide as the raw material and the lithium compound, the particle size of the manganese dioxide as the raw material is preferably 0.2 to 73 μm, more preferably 0.2 to 35 μm, and the particle size of one of the lithium compounds of lithium hydroxide, lithium nitrate and lithium oxalate is preferably 0.5 to 70 μm, more preferably 1 to 10 μm. The manganese dioxide is one of Electrolytic Manganese Dioxide (EMD) and Chemical Manganese Dioxide (CMD), preferably Electrolytic Manganese Dioxide (EMD). The crystal structure of manganese dioxide is alpha-MnO 2 、β-MnO 2 、 γ-MnO 2 。
Because the electrolytic manganese dioxide contains low-valence trivalent manganese and divalent manganese components, 1 to 30 weight percent of hydrogen peroxide is added into the electrolytic manganese dioxide, and evaporation drying treatment is carried out at a temperature of between 40 and 100 ℃, or the electrolytic manganese dioxide is subjected to heat treatment in advance for 1 to 40 hours, preferably 1 to 10 hours, at a temperature of between 200 and 400 ℃ in the air.
The temperature has certain influence on the product components during synthesis, and when the temperature t is more than 200 ℃ and less than or equal to 250 ℃, the reaction product is mainly LiMn 2 O 4 And gamma-MnO 2 At synthesis temperatures above 250 ℃ or MnO 2 After the raw materials are treated by hydrogen peroxide or heat in the air, the reaction product is mainly LiMn 2 O 4 With gamma and/or beta MnO 2 The complex of (1). No diffraction peak of LiOH in the x-ray spectrogram of the reaction product, and the x-ray diffraction spectrum of the product, the raw material and spinel LiMn 2 O 4 The X-ray diffraction spectrum data are compared as follows:TABLE 1X-ray diffraction spectra and original of the productsMaterial and spinel LiMn 2 O 4 Of X-ray diffraction spectrum
Data comparison Material 2 θ/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o LiOH 33/100 20/45 36/20 Li 2 O 34/100 56/40 67/20 β-MnO 2 29/100 37/55 57/55 γ-MnO 2 37/100 57/96 43/65 LiMn 2 O 4 19/10036/3844/33 product 37/10019/5129/6757/5421/42
In the product structure of the invention, 2 theta is the relative intensity (I/I) of the peaks at 21 DEG and 19 DEG o ) The ratio of (1: 1) - (1.7) and the relative intensity value of the peak of 2 theta =57 ° is 30-70.
The lithium manganese composite oxide having high capacity and excellent cycle characteristics according to the present invention can be used as a cathode active material for secondary batteries, such as rechargeable lithium batteries and lithium ion batteries, to manufacture secondary batteries. When the lithium-manganese composite oxide is used as an active cathode material of a lithium secondary battery, an electrode film is prepared, wherein the electrode comprises 75-90% of the lithium-manganese composite oxide cathode active material, 5-15% of conductive agent acetylene black or graphite and 5-10% of adhesive polytetrafluoroethylene emulsion, and an electrode plate (button cell electrode) or an electrode belt (barrel cell electrode) is prepared by adopting a rolling method; the anode of the battery is metallic lithium or lithium alloy or carbon material (which can allow lithium ions to be inserted or extracted). The electrolyte is known to those of ordinary skill in the art. The lithium salt is a mixed non-aqueous solution of lithium salt in one or two or more of organic solvents, such as Propylene Carbonate (PC), ethylene Carbonate (EC), ethylene glycol dimethyl ether (DME) and diethyl carbonate (DEC).For example LiClO with 1M electrolyte 4 Non-aqueous conductive electrolyte or 1MLiClO dissolved in mixed solvent of Propylene Carbonate (PC) and ethylene glycol dimethyl ether (DME) 4 A non-aqueous conductive electrolyte dissolved in PC and Ethylene Carbonate (EC) and DME. The cathode and the anode are isolated by adopting a porous diaphragm to prevent electron conduction, and the diaphragm is a 2400 polypropylene microporous diaphragm.
The performance test of the lithium manganese composite oxide cathode active material adopts a glass sealed flat plate electrode battery. The lithium secondary battery using the lithium manganese composite oxide of the present invention as a cathode active material is described above.
Lithium manganese composite oxide XLiMn for cathode active material of lithium secondary battery according to the present invention 2 O 4 Y gamma and/or beta MnO2, X is more than or equal to 0.5Y, X is more than or equal to 1 and less than or equal to 4, and has the advantages that:
1. the specific capacity of the material can reach 150-190mAh/g, the material has excellent cycle performance, the capacity retention rate in the charge-discharge cycle process is improved, and 50% capacity deep cycle can reach 400-600 times.
2. The composite oxide lithium secondary battery cathode active material can be used for nonaqueous organic electrolyte button lithium secondary batteries and cylinder lithium secondary batteries and batteries of lithium ions taking carbon as an anode, such as button 2025 type batteries, i.e., +/-16 multiplied by 1.1mm, the electrode capacity can reach 75mAh,4mAh discharge cycle can reach more than 400 times, 1mAh discharge cycle can reach 3000 times, the composite oxide lithium secondary battery cathode active material is used for button 2016 type batteries, i.e., +/-16 multiplied by 0.4mm electrode capacity can reach 40mAh, the AA type cylinder battery capacity can reach 690mAh, and can be cycled for 100 times.
The process method has the advantages of simple process and easy operation, and the capacity retention rate of the electrolytic manganese dioxide raw material in the charge-discharge cycle process can be improved by 15 percent after the electrolytic manganese dioxide is treated by hydrogen peroxide or heat treatment.
Figure 1 cycle life of the cell in example 1. 50% deep circulation, the abscissa is the circulation frequency, times; the ordinate is the discharge termination voltage, V.
Fig. 2 example 2 effect on cycle life of lithium manganese composite oxide synthesized with manganese dioxide treated with hydrogen peroxide.
100% DOD cycles, number of abscissa cycles, times; the ordinate is the discharge capacity, mAh/g.
a raw material MnO 2 And (4) treating with hydrogen peroxide.
b raw material MnO 2 Without hydrogen peroxide treatment.
Fig. 3 cycle life of the example 3 cell.
50% DOD cycles, number of cycles on the abscissa, times; the ordinate is the discharge termination voltage, V.
a raw material MnO 2 And (4) performing heat treatment.
b raw material MnO 2 Without heat treatment.
Fig. 4 example 4 charge and discharge cycles of an AA-type lithium secondary battery.
50% DOD cycles, number of abscissa cycles, times; the ordinate is the discharge termination voltage, V.
Figure 5 (a) cycle life of example 5 button cell.
Deep discharge id =2ic =1.8ma at 1 mAh.
Vc = 3.5-4.0V, and the abscissa represents the cycle number; the ordinate is the battery operating voltage, V.
Figure 5 (b) cycle life of example 5 button cell.
Deep discharge id =2ic =1.8ma at 4 mAh.
Vc = 3.5-4.0V, and the abscissa is the cycle number; the ordinate is the battery operating voltage, V.
Fig. 6 example 6 charge-discharge cycling of an AA-type lithium ion battery.
50% DOD cycles, number of cycles on the abscissa, times; the ordinate is the discharge termination voltage, V.
Fig. 7 is an X-ray diffraction spectrum of the lithium manganese composite oxide of the present invention.
The abscissa is 2 theta, the ordinate is Count (CPS), X-ray diffraction adopts a Cu target, 40KV and 50mA currents, the scanning speed is 6 degrees/minute, and the scanning range is 2 theta: 10-110 degrees.
The invention will be described in more detail hereinafter with reference to non-limiting examples, which are intended to assist the understanding of the invention and its advantages, the scope of the invention being not limited by these examples, but rather by the claims.
Example 1
In this example, a cathode active material lithium manganese composite oxide for a lithium secondary battery was XLIMn 2 O 4 .Yr-MnO 2 X =3y =1, 2 θ of characteristic peak: relative intensities (I/I) of peaks at 19 °,21 °, 29 °, 37 °, 57 °,21 °,19 ° o ) The ratio of (1: 1.1) and the relative intensity of the peak I/I at 57 DEG o Is 44.
The data of the X-ray diffraction spectrum are: 2 theta/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 37/10019/6921/6357/4429/38 anhydrous LiOH and Electrolytic Manganese Dioxide (EMD) are mixed thoroughly in a Li: mn atomic ratio = 1: 2.3, and the mixture is placed in an alumina crucible (or porcelain crucible) and heated in flowing air in a crucible furnace to a batch temperature of 250 c and held at a temperature of 250 c for 30 hours. The obtained product is used as a cathode active material of a lithium secondary battery and is mixed with acetylene black serving as a conductive agent and polytetrafluoroethylene emulsion serving as a binder, and the proportion (wt%) of the acetylene black to the polytetrafluoroethylene emulsion is 75: 15: 10. Rolling into 0.18mm film on a double-roller mill, andcutting to obtain 1.5-1.0cm 2 The cathode sheet of (2) is compounded with the stainless steel mesh, and the stainless steel mesh is used as a collector. The cathode prepared by the method, a metallic lithium anode and a diaphragm form a battery, and an electrolyte is added. The electrolyte composition is 1MLiClO 4 Dissolving in PC/DME (1: 1) organic solvent. The test cell was measured at 1mA/cm 2 Current density discharge of 0.5mA/cm 2 The initial discharge capacity is 8.6mAh, the specific capacity of the lithium manganese composite oxide active substance of the product is 171mAh/g, the charge-discharge voltage range is 4.0-2.0V, the cycle capacity retention rate is 82% after 10 times, the battery adopts 50% deep cycle, the cycle is 150 times, and the voltage reaches the lower limit of 2.0V. See fig. 1 for a cycle life curve for the cell. The cathode after circulation is analyzed by X-ray to obtain the structure of active material, and the diffraction angle and the surface distance d of three strongest peaks are as follows: see Table 2
TABLE 2 data of diffraction angles and d values of interplanar spacings of the three strongest peaks
After circulation before circulation
2θ 18.54 21.4 37.36 19.04 21.4 37.04
d 4.782 4.149 2.405 4.675 4.148 2.425
It can be seen that the positions of the three main peaks are substantially unchanged after cycling, and the 19 ° peak is slightly weakened, indicating that the structure of the active cathode material is stable.
Example 2
In this example, XLiMn composite oxide for a cathode active material of a lithium secondary battery was XLiMn 2 O 4 ·y (βMnO 2 And gamma-MuO 2 ) X is 1, Y is 1, characteristic peak 2 θ: relative intensities (I/I) of peaks at 19 °,21 °, 29 °, 37 °, 57 °,21 °,19 ° o ) The ratio of (A) to (B) is 1: 1.2,relative intensity of Peak (I/I) of 57 DEG o ) Is 54.
The data of the X-ray diffraction spectrum are: 2 theta/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 37/100 19/51 29/67 57/54 21/42
The synthesis is essentially the same as in example 1, except that the electrolytic manganese dioxide is treated with hydrogen peroxide before use, 70 ml of 10 wt% hydrogen peroxide is added to 42 g MnO 2 After being stirred uniformly, the mixture is dried at 75 ℃ for standby.
Anhydrous LiOH and Electrolytic Manganese Dioxide (EMD) were mixed well at an atomic ratio of Li to Mn = 1: 3.0, and the temperature was maintained at 300 ℃ for 40 hours. The manganese dioxide particle size was less than 35 μm and the LiOH particle size was less than 30 μm, and the resulting product was formed into cathode sheets and assembled into test cells for testing performance as described in example 1. MnO treatment by hydrogen peroxide 2 The product has improved cycle performance and specific capacity of 182mAh/g. The electrolyte was cycled 100% deep as in example 1, with a discharge current density of 1mA/cm 2 Charging current of 0.5mA/cm 2 See fig. 2 for the effect of the lithium manganese composite oxide synthesized with manganese dioxide treated with hydrogen peroxide on cycle life. EMD channel H can be seen 2 O 2 The lithium manganese composite oxide synthesized after treatment has better cycle performance.
Example 3
In this example, a lithium manganese composite oxide for a cathode active material of a lithium secondary battery was XLIMn 2 O 4 .Y(βMnO 2 And gamma-MnO 2 ) X is 1, Y is 2, characteristic peak 2 θ: relative intensities (I/I) of peaks at 19 °,21 °, 29 °, 37 °, 57 °,21 °,19 ° o ) The ratio of (1: 1.7) and the relative intensity of the peak I/I at 57 DEG o Is 69.
The data of the X-ray diffraction spectrum are: 2 theta/I/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 2θ/I/I o 37/100 29/74 19/38 57/69 43/40 21/23
The synthesis was carried out substantially as in example 1, except that electrolytic manganese dioxide was previously heat-treated in air at 370 ℃ for 2 hours.
Anhydrous LiOH and Electrolytic Manganese Dioxide (EMD) which had been previously heat-treated were thoroughly mixed in a ratio of Li to Mn (atomic ratio) = 1: 4, and the mixture was kept at 370 ℃ for 25 hours. MnO 2 The particle size of (b) is less than 73 μm, the particle size of LiOH is less than 70 μm, and the capacity of the obtained product is 150mAh/g. The cycle times can reach 600 times. The resultant was assembled into a battery according to the method of example 1, and the performance was tested, and the cycle was deeply charged and discharged at 50%, and the electrolyte and the charge and discharge current density were the same as those of example 1, as shown in fig. 3, the influence of the lithium manganese composite oxide synthesized from the manganese dioxide after heat treatment on the cycle life was observed, and it was found that the lithium manganese composite oxide synthesized from the electrolytic manganese dioxide after heat treatment had better cycle performance.
Example 4
The product obtained in example 1 was rolled into a 0.4mm electrode sheet according to the electrode ratio, and used as a cathode, a lithium-containing alloy as an anode, a 2400-type polypropylene microporous film as a separator, and 1MLiClO with PC: EC: DME (volume ratio 1: 2) as a solvent 4 The nonaqueous solution is used as an electrolyte. And assembling an AA type practical battery, and testing the capacity and the charge-discharge cycle of the battery. The discharge current was 60mA, the charge current was 30mA, with 50% deep charge-discharge cycling, test results: initial capacity 690mAh. Fig. 4 shows the charge-discharge cycle curve of AA-type lithium secondary battery.
Example 5
The product synthesized in example 3 was added with 10% of a conductive agent and 5% of a binder, and the balance was the product.Preparing into electrode plate of phi 16 × 1.1mm as cathode, lithium as anode, and 1MLiClO as electrolyte 4 The button cell is assembled by the PC-DME, and is charged and discharged by 4mAh, the current density is 1mA, the cycle times are more than 450 times, and the cycle times are more than 2500 times by 1 mAh. See figure 5 (a) 2025 button cell cycle life.
Example 6
The product synthesized in example 1 was used to prepare a belt electrode by the method of example 1, using a lithium-containing carbon material as an anode, and 1MLiClO 4 The solution of PC, EC and DME (volume ratio is 1: 2) is used as electrolyte to assemble the AA type lithium ion battery, the capacity is 400mAh, and the charging and discharging circulation curve of the AA type lithium ion battery is shown in figure 6.
Claims (7)
1. A composite Li-Mn oxide as cathode active material for secondary Li-battery is prepared from XLIMn 2 O 4 Y gamma and/or beta MnO2, X is more than or equal to 0.5Y, X is more than or equal to 1 and less than or equal to 4, and the structure of the LiMn is spinel 2 O 4 With gamma and/or beta MnO 2 The structural analysis of the X-ray diffraction spectrum of the composite oxide (1) under CuK alpha incidence shows that the ratio of 2 theta of a characteristic peak: 19 °,21 °, 29 °, 37 °, 57 °; relative intensity of peaks 21 DEG and 19 DEG (I/I) o ) A relative intensity of a peak of which the ratio of (1: 1) - (1.7) 2 theta =57 DEG is 30 < I/I o ＜70。
2. A process for preparing the composite Li-Mn oxide as the cathode active material of secondary Li-battery includes such steps as mixing the Li compound of lithium hydroxide, lithium nitrate or lithium oxalate with Mn dioxide in the atomic ratio of Li to Mn = 1: 2.2-4.0, and thermal insulating at 200-400 deg.C for 10-40 hr to obtain XLIMn oxide 2 O 4 ·YγAnd/or beta MnO2, X is more than or equal to 0.5Y, X is more than or equal to 1 and less than or equal to 4.
3. The method for preparing a lithium manganese complex oxide according to claim 2, characterized in that the particle size of the raw material manganese dioxide is 0.2 μm to 73 μm, and the particle size of one of lithium compounds of lithium hydroxide, lithium nitrate and lithium oxalate is 0.5 to 70 μm.
4. The method of manufacturing lithium manganese complex oxide according to claim 2, wherein said manganese dioxide is one of Electrolytic Manganese Dioxide (EMD) and Chemical Manganese Dioxide (CMD).
5. The method for preparing a lithium manganese complex oxide according to claim 4, characterized in that 1-30wt% hydrogen peroxide is added to Electrolytic Manganese Dioxide (EMD) and the evaporation is carried out at 40-100 ℃.
6. The method of manufacturing lithium manganese complex oxide according to claim 4, wherein the Electrolytic Manganese Dioxide (EMD) is previously heat-treated in air at 200 to 400 ℃ for 1 to 40 hours.
7. A lithium secondary battery using the lithium manganese composite oxide according to claim 1 as a cathode active material.
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| JP5226917B2 (en) * | 2000-01-21 | 2013-07-03 | 昭和電工株式会社 | Positive electrode active material, method for producing the same, and non-aqueous secondary battery using the same |
| CN1297020C (en) * | 2002-12-24 | 2007-01-24 | 中国科学院青海盐湖研究所 | Calicining process for high-quality lithium ion battery positive electrodes and calcining apparatus thereof |
| CN1324731C (en) * | 2003-07-15 | 2007-07-04 | 新乡无氧铜材总厂 | Preparation process of lithium manganese oxide cathode material for lithium ion battery |
| CN102403496B (en) * | 2011-12-16 | 2014-07-30 | 江南大学 | Composite cathode material of high-content lithium-ion battery and synthesis method for composite cathode material |
| CN110911676B (en) * | 2018-09-18 | 2021-09-10 | 瑞海泊(青岛)能源科技有限公司 | Positive electrode material for lithium ion battery, preparation method and application thereof, and battery |
| CN114843445A (en) * | 2022-06-21 | 2022-08-02 | 江门市宏力能源有限公司 | Lithium-manganese battery positive electrode and preparation method thereof |
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| GB2221213A (en) * | 1988-07-12 | 1990-01-31 | Csir | Synthesizing lithium manganese oxide |
| GB2245264A (en) * | 1990-06-18 | 1992-01-02 | Technology Finance Corp | Lithium manganese oxide |
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| GB2221213A (en) * | 1988-07-12 | 1990-01-31 | Csir | Synthesizing lithium manganese oxide |
| GB2245264A (en) * | 1990-06-18 | 1992-01-02 | Technology Finance Corp | Lithium manganese oxide |
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